Grappa - a machine learned molecular mechanics force field.

Simulating large molecular systems over long timescales requires force fields that are both accurate and efficient. In recent years, E(3) equivariant neural networks have lifted the tension between computational efficiency and accuracy of force fields, but they are still several orders of magnitude more expensive than established molecular mechanics (MM) force fields. Here, we propose Grappa, a machine learning framework to predict MM parameters from the molecular graph, employing a graph attentional neural network and a transformer with symmetry-preserving positional encoding.

Molecular engineering of supramolecular polymer adhesive with confined water and a single crown ether.

Here, we report a water-induced supramolecular polymer adhesive formed from confined water and an intrinsically amphiphilic macrocyclic self-assembly in a nanophase-separated structure. The selenium-containing crown ether macrocycle, featuring a strong hydrophilic hydrogen-bond receptor (selenoxide) and a synergistic hydrophobic selenium-substituted crown core, confines water within a segregated, interdigitated architecture. While water molecules typically freeze around 0 °C, the confined water in this supramolecular polymer remains in a liquid-like state down to -80 °C.

Protein-Specific Crowding Accelerates Aging in Protein Condensates.

Macromolecular crowding agents, such as poly(ethylene glycol) (PEG), are often used to mimic cellular cytoplasm in protein assembly studies. Despite the perception that crowding agents have an inert nature, we demonstrate and quantitatively explore the diverse effects of PEG on the phase separation and maturation of protein condensates. We use two model proteins, the FG domain of Nup98 and bovine serum albumin (BSA), which represent an intrinsically disordered protein and a protein with a well-established secondary structure, respectively.

Acid-induced fluorescence enhancement of piperazinylphenyl-substituted nanographene.

A dibenzo[,]ovalene (DBOV) derivative bay-substituted with two piperazinylphenyl (PZP) groups (DBOV-PZP) was synthesized. Comprehensive investigations of its photophysical properties revealed acid-induced fluorescence enhancement through the protonation of PZP units, leading to the suppression of the photoinduced electron transfer. These results pave the way towards "turn-on" type nanographenes for biosensing and optical imaging.

Synthesis and photoinduced behavior of DPP-anchored nitronyl nitroxides: a multifaceted approach.

Understanding and controlling spin dynamics in organic dyes is of significant scientific and technological interest. The investigation of 2,5-dihydropyrrolo[4,3-]pyrrolo-1,4-dione derivatives (DPPs), one of the most widely used dyes in many fields, has so far been limited to closed-shell molecules. We present a comprehensive joint experimental and computational study of DPP derivatives covalently linked to two nitronyl nitroxide radicals (DPP-NN).

Mechanistic insights into radical formation and functionalization in copper/-fluorobenzenesulfonimide radical-relay reactions.

Copper-catalysed radical-relay reactions that employ -fluorobenzenesulfonimide (NFSI) as the oxidant have emerged as highly effective methods for C(sp)-H functionalization. Herein, computational studies are paired with experimental data to investigate a series of key mechanistic features of these reactions, with a focus on issues related to site-selectivity, enantioselectivity, and C-H substrate scope. (1) The full reaction energetics of enantioselective benzylic C-H cyanation are probed, and an adduct between Cu and the -sulfonimidyl radical (˙NSI) is implicated as the species that promotes hydrogen-atom transfer (HAT) from the C-H substrate.

Molecular transport and water condensation inside mesopores with wettability step gradients.

The wettabilities of nanoscale porous surfaces play important roles in the context of molecular and fluid transport or oil-water separation. The wettability pattern along a nanopore strongly influences fluid distribution throughout the membrane. Mesoporous silica thin films with gradually adjusted wettabilities were fabricated cocondensation.

Zigzag-Edged Polycyclic Aromatic Hydrocarbons from Benzo[m]tetraphene Precursors.

A series of zigzag-edged polycyclic aromatic hydrocarbons (PAHs) (Z1-Z3) were synthesized from 2,12-dibromo-7,14-diphenyl-benzo[m]tetraphene (9) as a versatile building block. Their structures were unambiguously confirmed by laser desorption/ionization time-of-flight mass spectrometry, H NMR, Raman, and Fourier-transformed infrared (FTIR) spectroscopies as well as scanning tunneling microscopy. The fingerprint vibrational modes were elucidated with theoretical support.

Using coherent X-rays to follow dynamics in amorphous ices.

Amorphous solid water plays an important role in our overall understanding of water's phase diagram. X-ray scattering is an important tool for characterising the different states of water, and modern storage ring and XFEL facilities have opened up new pathways to simultaneously study structure and dynamics. Here, X-ray photon correlation spectroscopy (XPCS) was used to study the dynamics of high-density amorphous (HDA) ice upon heating.

Synthesis of zigzag- and fjord-edged nanographene with dual amplified spontaneous emission.

We report the synthesis of a dibenzodinaphthocoronene (DBDNC) derivative as a novel nanographene with armchair, zigzag, and fjord edges, which was characterized by NMR and X-ray crystallography as well as infrared (IR) and Raman spectroscopies. Ultrafast transient absorption (TA) spectroscopy revealed the presence of stimulated emission signals at 655 nm and 710 nm with a relatively long lifetime, which resulted in dual amplified spontaneous emission (ASE) bands under ns-pulsed excitation, indicating the promise of DBNDC as a near-infrared (NIR) fluorophore for photonics. Our results provide new insight into the design of nanographene with intriguing optical properties by incorporating fjord edges.

Charge storage mechanisms of a π-d conjugated polymer for advanced alkali-ion battery anodes.

The demand for fast-charging metal-ion batteries underlines the importance of anodes that work at high currents with no risk of dendrite formation. NiBTA, a one-dimensional Ni-based polymer derived from benzenetetramine (BTA), is a recently proposed promising material for safe fast-charging batteries. However, its charge-discharge mechanisms remained unclear and controversial.

The role of structural order in heterogeneous ice nucleation.

The freezing of water into ice is a key process that is still not fully understood. It generally requires an impurity of some description to initiate the heterogeneous nucleation of the ice crystals. The molecular structure, as well as the extent of structural order within the impurity in question, both play an essential role in determining its effectiveness.

Assembly of iron oxide nanosheets at the air-water interface by leucine-histidine peptides.

The fabrication of inorganic nanomaterials is important for a wide range of disciplines. While many purely inorganic synthetic routes have enabled a manifold of nanostructures under well-controlled conditions, organisms have the ability to synthesize structures under ambient conditions. For example, magnetotactic bacteria, can synthesize tiny 'compass needles' of magnetite (FeO).

RNA-inspired intramolecular transesterification accelerates the hydrolysis of polyethylene-like polyphosphoesters.

To synthesize new (bio)degradable alternatives to commodity polymers, adapting natural motives can be a promising approach. We present the synthesis and characterization of degradable polyethylene (PE)-like polyphosphoesters, which exhibit increased degradation rates due to an intra-molecular transesterification similar to RNA. An α,ω-diene monomer was synthesized in three steps starting from readily available compounds.

Chemoselective cysteine or disulfide modification single atom substitution in chloromethyl acryl reagents.

The development of bioconjugation chemistry has enabled the combination of various synthetic functionalities to proteins, giving rise to new classes of protein conjugates with functions well beyond what Nature can provide. Despite the progress in bioconjugation chemistry, there are no reagents developed to date where the reactivity can be tuned in a user-defined fashion to address different amino acid residues in proteins. Here, we report that 2-chloromethyl acryl reagents can serve as a simple yet versatile platform for selective protein modification at cysteine or disulfide sites by tuning their inherent electronic properties through the amide or ester linkage.

Targeted Repolarization of Tumor-Associated Macrophages via Imidazoquinoline-Linked Nanobodies.

Tumor-associated macrophages (TAMs) promote the immune suppressive microenvironment inside tumors and are, therefore, considered as a promising target for the next generation of cancer immunotherapies. To repolarize their phenotype into a tumoricidal state, the Toll-like receptor 7/8 agonist imidazoquinoline IMDQ is site-specifically and quantitatively coupled to single chain antibody fragments, so-called nanobodies, targeting the macrophage mannose receptor (MMR) on TAMs. Intravenous injection of these conjugates result in a tumor- and cell-specific delivery of IMDQ into MMR TAMs, causing a significant decline in tumor growth.

Novel Opportunities for Cathepsin S Inhibitors in Cancer Immunotherapy by Nanocarrier-Mediated Delivery.

Cathepsin S (CatS) is a secreted cysteine protease that cleaves certain extracellular matrix proteins, regulates antigen presentation in antigen-presenting cells (APC), and promotes M2-type macrophage and dendritic cell polarization. CatS is overexpressed in many solid cancers, and overall, it appears to promote an immune-suppressive and tumor-promoting microenvironment. While most data suggest that CatS inhibition or knockdown promotes anti-cancer immunity, cell-specific inhibition, especially in myeloid cells, appears to be important for therapeutic efficacy.

Hierarchically Structured Porous Piezoelectric Polymer Nanofibers for Energy Harvesting.

Hierarchically porous piezoelectric polymer nanofibers are prepared through precise control over the thermodynamics and kinetics of liquid-liquid phase separation of nonsolvent (water) in poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) solution. Hierarchy is achieved by fabricating fibers with pores only on the surface of the fiber, or pores only inside the fiber with a closed surface, or pores that are homogeneously distributed in both the volume and surface of the nanofiber. For the fabrication of hierarchically porous nanofibers, guidelines are formulated.

Doping free transfer of graphene using aqueous ammonia flow.

Doping-free transfer of graphene produced by catalytic chemical vapor deposition (CVD) on copper foil, is still a technical challenge since unintentional doping of the transferred graphene layer yields an uncontrolled shift of Dirac point in graphene-based field-effect transistors (FETs). Typically, CVD graphene is released from the growth template by etching of the template, copper. During the etching process, ions adhere to the graphene layer resulting in unintentional doping.

Room-temperature solution-phase epitaxial nucleation of PbS quantum dots on rutile TiO (100).

Owing to its simplicity and versatility, the successive ionic layer adsorption and reaction (SILAR) method is increasingly being employed to develop low-cost hetero-nanostructured sensitized oxide systems for solar energy conversion, such as solar cells and solar fuels schemes. Understanding the nature of the SILAR quantum dot (QD) nucleation and growth on an insulating oxide is then critical as it will determine the QD density and spatial distribution, as well as the optoelectronic properties of the QD/oxide interfaces ( QD bandgap onset). Here, we demonstrate epitaxial nucleation of lead sulfide (PbS) QDs onto a planar rutile titanium dioxide (100) surface employing the SILAR method.

Nanostructured carbons containing FeNi/NiFeO supported over N-doped carbon nanofibers for oxygen reduction and evolution reactions.

Non-precious metal-based electrocatalysts on carbon materials with high durability and low cost have been developed to ameliorate the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) for electrochemical energy applications such as in fuel cells and water electrolysis. Herein, two different morphologies of FeNi/NiFeO supported over hierarchical N-doped carbons were achieved carbonization of the polymer nanofibers by controlling the ratio of metal salts to melamine: a mixture of carbon nanotubes (CNTs) and graphene nanotubes (GNTs) supported over carbon nanofibers (CNFs) with spherical FeNi encapsulated at the tips (G/CNT@NCNF, 1 : 3), and graphene sheets wrapped CNFs with embedded needle-like FeNi (GS@NCNF, 2 : 3). G/CNT@NCNF shows excellent ORR activity (on-set potential: 0.

Flow-Induced Long-Term Stable Slippery Surfaces.

Slippery lubricant-infused surfaces allow easy removal of liquid droplets on surfaces. They consist of textured or porous substrates infiltrated with a chemically compatible lubricant. Capillary forces help to keep the lubricant in place.

Chemical Dopants on Edge of Holey Graphene Accelerate Electrochemical Hydrogen Evolution Reaction.

Carbon-based metal-free catalysts for the hydrogen evolution reaction (HER) are essential for the development of a sustainable hydrogen society. Identification of the active sites in heterogeneous catalysis is key for the rational design of low-cost and efficient catalysts. Here, by fabricating holey graphene with chemically dopants, the atomic-level mechanism for accelerating HER by chemical dopants is unveiled, through elemental mapping with atomistic characterizations, scanning electrochemical cell microscopy (SECCM), and density functional theory (DFT) calculations.

Prevention of Dominant IgG Adsorption on Nanocarriers in IgG-Enriched Blood Plasma by Clusterin Precoating.

Nanocarriers for medical applications must work reliably within organisms, independent of the individual differences in the blood proteome. Variation in the blood proteome, such as immunoglobulin levels, is a result of environmental, nutrition, and constitution conditions. This variation, however, should not influence the behavior of nanocarriers in biological media.